Semiconductor device having barrier metal layer

ABSTRACT

According to one embodiment, a semiconductor device having an interlayer insulating film, a molybdenum containing layer, a barrier metal layer and a plug material layer is provided. The interlayer insulating film is formed on a substrate or on a conductive layer formed on a substrate. The interlayer insulating film has a hole reaching the substrate or the conductive layer. The molybdenum containing layer is formed in the substrate or in the conductive layer at a bottom portion of the hole. The barrier metal layer is formed on the molybdenum containing layer and on a side surface of the hole. A portion of the barrier metal layer is formed on the side surface contains at least molybdenum. A portion of the barrier metal layer is formed on the molybdenum containing layer includes at least a molybdenum silicate nitride film. The plug material layer is formed via the barrier metal layer.

CROSS-REFERENCE TO RELATED APPLICATION

This application is based upon and claims the benefit of priority fromthe prior Japanese Patent Application No. 2012-198631, filed on Sep. 10,2012, the entire contents of which are incorporated herein by reference.

FIELD

Embodiments described herein relate generally to a semiconductor devicehaving a barrier metal layer.

BACKGROUND

In order to reduce wiring resistance and manufacturing cost of LSI, itis preferable that a plug interconnection be formed of a plug materialand a barrier metal material with low resistance and low cost. Anexample of the plug material may be copper (Cu). In addition, an exampleof the barrier metal material may be tungsten nitride (WN). Whentungsten (W) is used as the plug material, main components of the plugmaterial and the barrier metal material are the same metal so that themanufacturing cost is further reduced. However, when a tungsten nitridefilm is formed on a silicon (Si) substrate as the barrier metalmaterial, silicon nitride is stable more than tungsten nitride.Formation of the tungsten nitride film may cause a problem that asilicon nitride film is formed in the silicon substrate so thatelectrical contact can not be obtained between the silicon substrate andthe plug interconnection. The same problem may occur when aninterconnection other than the plug interconnection, or an electrodesuch as a gate electrode, a floating gate, and a control gate is formed.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional view of a semiconductor device of a firstembodiment.

FIG. 2 is a cross-sectional view illustrating a semiconductor device ofa modification of the first embodiment.

FIG. 3A to FIG. 31 are cross-sectional views illustrating steps of amethod of manufacturing the semiconductor device according to the firstembodiment.

FIG. 4 is a graph illustrating change of standard free energy of variouskinds of silicide with temperature.

FIG. 5 is a cross-sectional view of a semiconductor device of anothermodification of the first embodiment.

FIG. 6 is a cross-sectional view illustrating a semiconductor device ofstill another modification of the first embodiment.

FIG. 7 is a cross-sectional view illustrating a semiconductor device ofa second embodiment.

FIG. 8 is a cross-sectional view illustrating a semiconductor device ofa third embodiment.

FIG. 9 is a cross-sectional view illustrating a semiconductor device ofa fourth embodiment.

FIG. 10 is a cross-sectional view illustrating a semiconductor device ofa fifth embodiment.

FIG. 11A to FIG. 11F are cross-sectional views illustrating steps of amethod of manufacturing the semiconductor device according to the fifthembodiment.

FIG. 12A to FIG. 12C are cross-sectional views illustratingsemiconductor devices of respective modifications of the fifthembodiment.

FIG. 13 is a cross-sectional view illustrating an modifications in whichthe semiconductor device of the fifth embodiment is applied to aNAND-type memory.

DETAILED DESCRIPTION

According to one embodiment, a semiconductor device having an interlayerinsulating film, a molybdenum containing layer, a barrier metal layerand a plug material layer is provided. The interlayer insulating film isformed on a substrate or on a conductive layer containing silicon formedon a substrate. The interlayer insulating film has a hole reaching thesubstrate or the conductive layer. The molybdenum containing layer isformed in the substrate or in the conductive layer at a bottom portionof the hole. The barrier metal layer is formed on the molybdenumcontaining layer and on a side surface of the hole. A portion of thebarrier metal layer is formed on the side surface contains at leastmolybdenum. A portion of the barrier metal layer is formed on themolybdenum containing layer includes at least a molybdenum silicatenitride film. The plug material layer is formed in the hole through thebarrier metal layer.

Hereinafter, further embodiments will be described with reference to thedrawings.

In the drawings, the same reference numerals denote the same or similarportions respectively.

A first embodiment will be described with reference to FIG. 1.

FIG. 1 is a cross-sectional view illustrating a structure of asemiconductor device according to a first embodiment which focuses across section of a contact plug 100 constituting the semiconductordevice.

The semiconductor device of FIG. 1 has a substrate 101, a molybdenumsilicide layer (hereinafter referred to as “MoSi_(X) layer”) 102,interlayer insulating films 111, 112, a molybdenum silicate nitride film(hereinafter referred to as “MoSiON film”) 121, a molybdenum oxynitridefilm (hereinafter referred to as “MoON film”) 122, a plug material layer123, and a wiring layer 124. The contact plug 100 is configured by theMoSi_(X) layer 102, the MoSiON film 121, the MoON film 122, and the plugmaterial layer 123.

For example, the substrate 101 is a semiconductor substrate such as asilicon (Si) substrate. FIG. 1 illustrates an X direction, a Y directionand a Z direction. The X direction and the Y direction are parallel to amain surface of the substrate 101 and perpendicular to each other. The Zdirection is parallel to the main surface of the substrate 101. Thesubstrate 101 may be an SOI (Semiconductor On Insulator) substrate inwhich an embedded insulating film and a semiconductor layer are formedon a semiconductor substrate in this order. An example of thesemiconductor substrate and the semiconductor layer may be a silicon(Si) layer.

The interlayer insulating films 111, 112 are formed on the substrate 101in this order. The interlayer insulating film 111 has a contact hole H₁formed to reach the substrate 101. The interlayer insulating films 111,112 are, for example, a silicon dioxide film (SiO₂).

The MoSi_(X) layer 102 is formed to extend into a surface region of thesubstrate 101 from a bottom portion of the contact hole H₁. In otherwords, the MoSi_(X) layer 102 is formed on a surface region of thesubstrate. The MoSi_(X) layer 102 is a molybdenum containing layer.

The MoSiON film 121 is formed on the MoSi_(X) layer 102 at the bottomportion of the contact hole H₁. The MoSiON film 121 is denoted by aMo_(X1)Si_(X2)O_(X3)N_(X4) film 121, specifically. The MoON film 122 isformed on a side surface of the contact hole H₁. The MoSiON film 121 andthe MoON film 122 compose a barrier metal layer containing molybdenum.

The plug material layer 123 is formed in the contact hole H₁ through theMoSiON film 121 and the MoON film 122 to be embedded inside the contacthole H₁. The plug material layer 123 is, for example, a molybdenum (Mo)layer.

The wiring layer 124 is formed on the plug material layer 123 and theinterlayer insulating film 111. The wiring layer 124 is, for example, acopper (Cu) layer or an aluminum (Al) layer. The wiring layer 124 iscovered with the interlayer insulating film 112.

The wiring layer 124 shown in FIG. 1 may be formed of the same materialas that of the plug material layer 123, as illustrated in FIG. 2. FIG. 2is a cross-sectional view illustrating a structure of a semiconductordevice of a modification of the first embodiment described above.According to the structure of a contact plug 100 a of FIG. 2, it ispossible to reduce the number of manufacturing steps and the cost ofwiring process.

A method of manufacturing the semiconductor device according to thefirst embodiment will be described with reference to FIG. 3A to FIG. 31.

FIG. 3A to FIG. 31 are cross-sectional views illustrating steps of themethod of manufacturing the semiconductor device according to the firstembodiment.

As illustrated in FIG. 3A, an interlayer insulating film 111 is formedon a substrate 101, and a surface of the interlayer insulating film 111is flattened by chemical mechanical polishing (CMP).

In addition, as illustrated in FIG. 3B, a contact hole H₁ reaching thesubstrate 101 is formed in the interlayer insulating film 111.

Then, as illustrated in FIG. 3C, a MoN film (a molybdenum nitride film)201 is laminated on a whole surface including a portion of the mainsurface of the substrate 101 by physical vapor deposition (PVD),chemical vapor deposition (CVD) or atomic layer deposition (ALD). TheMoN film 201 is formed on a bottom surface and a side surface of thecontact hole H₁.

As illustrated in FIG. 3D, the surface of the MoN film 201 is oxidizedto form a MoO_(X) film (a molybdenum oxide film) 202 on the surface ofthe MoN film 201. The MoO_(X) film 202 is formed on the bottom surfaceand the side surface of the contact hole H₁ through the MoN film 201. Alaminated film including the MoN film 201 and the MoO_(X) film 202composes a barrier metal layer containing molybdenum.

The lamination process for the MoN film 201 and the oxidation processfor the surface of the MoN film 201 may be performed in the samechamber, or may be performed in separate chambers connected commonly toa spare chamber which can be vacuumized. The chambers may be released tothe atmosphere between the processes.

The oxidation process for the surface of the MoN film 201 is performedat the same temperature as that of the lamination process for the MoNfilm 201, for example, at a temperature equal to or higher than 400° C.,in an atmosphere of decompression or atmospheric pressure. Hereinafter,a heat treatment at the oxidation process is referred to as a first heattreatment. The oxidation process for the surface of the MoN film 201 maybe performed using plasma.

Then, as illustrated in FIG. 3E, a heat treatment of the substrate 101is performed at a temperature higher than the temperature of the firstheat treatment, for example, at a temperature equal to or high than 500°C. As a result, a MoSi_(X) layer 102 is formed to extend into a surfaceregion of the substrate 101 from the bottom portion of the contact holeH₁. In other words, the MoSi_(X) layer 102 is formed on a surface regionof the substrate 101. Further, by the heat treatment, the MoN film 201and the MoO_(X) film 202 are changed into a MoON film 122, and siliconcontained in the substrate 101 is also diffused into a portion of theMoON film 122 existing on the bottom portion of the contact hole H₁.Accordingly, a MoSiON film 121 and the MoON film 122 are formed on thebottom portion and on the side surface of the contact hole H₁,respectively. Hereinafter, the heat treatment is referred to as a secondheat treatment.

The first and the second heat treatment may be integrated into one heattreatment. In this case, the heat treatment is performed, for example,at a temperature equal to or higher than 500° C. In this case, theprocess of oxygenating the surface of the MoN film 201, the process offorming the MoSi_(X) layer 102, and the process of changing the MoN film201 and the MoO_(X) film 202 into the MoSiON film 121 and the MoON film122 progress simultaneously. It is possible to reduce the number of heattreatments by such a heat treatment.

As illustrated in FIG. 3F, a material of a plug material layer 123 islaminated on a whole surface including a portion the main surface of thesubstrate 101 by CVD. The material of a plug material layer 123 isformed to includ the inside of the contact hole H₁. In addition, asillustrated in FIG. 3G, the surface of the material is flattened by CMP.As a result, the plug material layer 123 is formed in the contact holeH₁ via the MoSiON film 121 and the MoON film 122. A surplus portion ofthe MoON film 122 formed outside the contact hole H₁ is removed by theflattening in the step of FIG. 3G.

Then, as illustrated in FIG. 3H, a wiring layer 124 is formed on theplug material layer 123 and the interlayer insulating film 111. Asillustrated in FIG. 3H, an interlayer insulating film 112 is formed onthe whole surface to cover the wiring layer 124. Subsequently, variousvia-plugs, wiring layers, and interlayer insulating films are formed. Insuch a manner, the semiconductor device shown in FIG. 1 is manufactured.

Alternatively, as illustrated in FIG. 31, a wiring layer correspondingto the wiring layer 124 of FIG. 3H may be formed of the same material asthat of the plug material layer 123 simultaneously with formation of theplug material layer 123, after the step of FIG. 3E. In this case, thesemiconductor device of FIG. 2 is manufactured. In this case, asillustrated in FIG. 31, a portion of the plug material layer 123corresponding to the wiring layer 124 of FIG. 3H is formed above theinterlayer insulating film 111 partially via the MoON film 122. The MoONfilm 122 is formed in the same pattern as the plug material layer 123 byetching.

The step of FIG. 3E will be described in detail with reference to FIG.4. Specifically, the reason why the MoSi_(X) layer 102 is formed toextend into the surface region of the substrate 101 from the bottomportion of the contact hole H₁, and the reason why the MoN film 201 andthe MoO_(X) film 202 are changed into the MoSiON film 121 and the MoONfilm 122 will be described.

FIG. 4 is a graph illustrating temperature characteristics of standardfree energy ΔG of various kinds of silicide.

In FIG. 4, straight lines A to E represent standard free energy ΔG ofWSi₂, W₅Si₃, MoSi₂, Mo₅Si₃, and Si₃N₄, respectively. As illustrated inFIG. 4, both of ΔG of WSi₂ and W₅Si₃ are larger than ΔG of Si₃N₄. Thus,when a WN film is formed on a silicon (Si) substrate, SiN is stabilizedmore than WN and the SiN film is formed in the silicon substrateaccordingly. As result, electrical contact can not be obtained betweenthe silicon substrate and the contact plug. WN cannot be used as abarrier metal material to be used when a contact plug is formed on asilicon substrate.

ΔG of Mo₅Si₃ becomes smaller than ΔG of Si₃N₄ at about 400° C. orhigher. Accordingly, when a MoN film is formed on a silicon substrate atabout 400° C. or higher, it is possible to avoid forming a SiN film in asilicon substrate. Accordingly, in the embodiment, the laminationprocess for the MoN film 201 of FIG. 3D is performed at 400° C. orhigher.

In this case, MoN is unstable in energy. Accordingly, when a contactplug is formed of a MoN film and a molybdenum (Mo) layer as a plugmaterial layer, both of the MoN film and the molybdenum layer becomesilicide. In the embodiment, in order to suppress such silicidation, thesurface of the MoN film 201 is oxidized to form the MoO_(X) film 202 asillustrated in FIG. 3D.

As illustrated in FIG. 3E, the MoN film 201 and the MoO_(X) film 202 ofFIG. 3D are changed into the MoON film 122 and the MoSiON film 121 andare stabilized. Nitrogen (N) atoms and oxygen (O) atoms in the MoON film122 and the MoSiON film 121 are derived from nitrogen atoms contained inthe MoN film 201 and oxygen atoms contained in the MoO_(X) film 202. Inaddition, silicon (Si) atoms of the MoSiON film 121 are silicon atomswhich are diffused from the silicon substrate 101.

Molybdenum atoms contained in the MoN film 201 in the vicinity of thesilicon substrate 101 are diffused into the silicon substrate 101 toform the MoSi_(X) layer 102.

Accordingly, in the step of FIG. 3E, the MoSi_(X) layer 102 is formed toextend into the surface region of the substrate 101 from the bottomportion of the contact hole H₁, and the MoN film 201 and the MoO_(X)film 202 are changed into the MoSiON film 121 and the MoON film 122.

FIG. 5 is a cross-sectional view illustrating a structure of asemiconductor device of another modification of the first embodiment. Inthe step of FIG. 3E, silicon atoms in the silicon substrate 101 may bediffused to the MoON film 122 of the side surface of the contact holeH₁. In this case, a semiconductor device illustrated in FIG. 5 ismanufactured. In FIG. 5, a MoSiON film 121 is formed on the bottomportion of a contact hole H₁ and on a portion of the side surface of thecontact hole H₁.

FIG. 6 is a cross-sectional view illustrating a structure of stillanother modification of the first embodiment. In the step of FIG. 3E,there is a case in which the MoN film 201 and the MoO_(X) film 202 shownin FIG. 3D are not changed into the MoSiON film 121 and the MoON film122 wholly but a portion of the MoO_(X) film 202 remains. In this case,a semiconductor device illustrated in FIG. 6 is manufactured. In FIG. 6,a portion of the MoO_(X) film 202 remains between a MoON film 122 and aplug material layer 123.

The MoON film may be formed as the barrier metal layer in the steps ofFIGS. 3C and 3D, instead of forming the laminated film including the MoNfilm 201 and the MoO_(X) film 202. The MoON film is a barrier metallayer containing molybdenum.

As described above, in the embodiment, the MoSiON film 121 and the MoONfilm 122 are used as the barrier metal layer. Any of the MoSiON film121, the MoON film 122, and the molybdenum layer has low resistance.According to the embodiment, it is possible to realize a contact plugwith low resistance.

Molybdenum is relatively inexpensively available. Thus, according to theembodiment, it is possible to realize a contact plug with low cost. Anyof the barrier metal layers 121, 122 and the plug material layer 123 ismainly based on molybdenum. According to the embodiment, it is possibleto further reduce the cost of the contact plug.

In the embodiment, the MoN film 201 and the MoO_(X) film 202 are formedin this order on the bottom surface and the side surface of the contacthole H₁, and the barrier metal layers 121, 122 are formed from the MoNfilm 201 and the MoO_(X) film 202. Thus, according to the embodiment, itis possible to suppress forming a SiN film between the substrate 101 andthe plug material layer 123.

In the embodiment, the plug material layer 123 may be formed of amaterial other than molybdenum (Mo). As such a material, relativelyinexpensively available copper (Cu), aluminum (Al), and tungsten (W) maybe used. For example, when the structure of FIG. 2 is employed, it ispreferable that the plug material layer 123 be formed of copper oraluminum. As other examples of the material for the plug material layer123, ruthenium (Ru) and tantalum (Ta) may be used. The plug materiallayer 123 may be formed of single metal or may be formed of alloy.

The substrate 101 may be a semiconductor substrate other than a siliconsubstrate. When the substrate 101 is the SOI substrate, thesemiconductor layer of the SOI substrate may be a semiconductor layerother than the silicon layer. As an example of the semiconductor whichcomposes the semiconductor substrate and the semiconductor layer,silicon germanium (SiGe) may be used.

FIG. 7 illustrates a structure of a semiconductor device of a secondembodiment, which focuses a via-plug constituting the semiconductordevice.

The semiconductor device of FIG. 7 has a molybdenum (Mo) containinglayer 301, a MoSiON film 311, a MoON film 312, a plug material layer313, a wiring layer 314, and an interlayer insulating film 113, inaddition to the configuration of the contact plug 100 illustrated inFIG. 1. A via-plug 300 is composed of the molybdenum (Mo) containinglayer 301, the MoSiON film 311, the MoON film 312, and the plug materiallayer 313.

In FIG. 7, a via-hole H₂ is formed in an interlayer insulating film 112.The via-hole H₂ is formed to reach a wiring layer 124. The wiring layer124 is, for example, a polysilicon layer. The wiring layer 124 is aconductive layer.

The molybdenum containing layer 301 is formed to extend into a surfaceportion of the wiring layer 124 from a bottom portion of the via-holeH₂. The molybdenum containing layer 301 may be a MoSi_(X) layer.

Each of the MoSiON film 311 and the MoON film 312 is formed on thebottom portion and on a side surface of the via-hole H₂. The MoSiON film311 and the MoON film 312 are a barrier metal layer containingmolybdenum.

The plug material layer 313 is formed in the via-hole H₂ via the MoSiONfilm 311 and the MoON film 312. The plug material layer 313 is, forexample, a molybdenum (Mo) layer.

The wiring layer 314 is formed on the plug material layer 313 and theinterlayer insulating film 112. The wiring layer 314 is, for example, acopper (Cu) layer or an aluminum (Al) layer. The wiring layer 314 iscovered with the interlayer insulating film 113.

As described above, the via-plug 300 of FIG. 7 has the same structure asthat of the contact plug 100 of FIG. 1. Thus, according to theembodiment, it is possible to realize a via-plug with low resistance andlow cost, similarly to the first embodiment. The semiconductor device ofthe embodiment can be manufactured by the same manufacturing method asthat of the semiconductor device of the first embodiment.

The via-plug 300 of the embodiment may have the same structure as thatof the contact plug 100 a of FIG. 2.

The wiring layer 124 of the embodiment may be the semiconductor layerother than the silicon layer, similarly to the case of the substrate 101of the first embodiment. The wiring layer 124 of the embodiment may be alaminated film including a metal layer and a semiconductor layer formedon the metal layer.

FIG. 8 illustrates a structure of a semiconductor device of a thirdembodiment, which focuses a portion including a contact plug (a gatecontact) constituting the semiconductor device.

The semiconductor device of FIG. 8 has a MOSFET 400 having a gateinsulating film 401, a gate electrode 402, a side wall insulating film403, and a source/drain diffusion layers 404, a molybdenum containinglayer 411, a MoSiON film 421, a MoON film 422, a plug material layer423, and a wiring layer 424, in addition to the configuration of thesemiconductor device illustrated in FIG. 1. The configuration of thesemiconductor device of FIG. 1 is not illustrated in FIG. 8 partially. Avia-plug 400 a is composed of the molybdenum containing layer 411, theMoSiON film 421, the MoON film 422, and the plug material layer 423.

The gate electrode 402 is formed on a substrate 101 via the gateinsulating film 401. The gate electrode 402 is, for example, apolysilicon layer. The gate electrode 402 is a conductive layer. Theside wall insulating film 403 is formed on a side surface of the gateelectrode 402. The source/drain diffusion layers 404 are formed in asubstrate 101 so as to interpose the gate electrode 402. The MOSFET 400of FIG. 8 is covered with an interlayer insulating film 111.

A contact hole H₃ is formed in the interlayer insulating film 111. Thecontact hole H₃ is formed to reach the gate electrode 402.

The molybdenum containing layer 411 is formed into a surface portion ofthe gate electrode 402 from a bottom portion of the contact hole H₃. Themolybdenum containing layer 411 is, for example, a MoSi_(X) layer.

The MoSiON film 421 and the MoON film 422 are formed on the bottomportion and on the side surface of the contact hole H₃, respectively.The MoSiON film 421 and the MoON film 422 are a barrier metal layercontaining molybdenum.

The plug material layer 423 is formed in the contact hole H₃ via theMoSiON film 421 and the MoON film 422. The plug material layer 423 is,for example, a molybdenum layer.

The wiring layer 424 is formed on the plug material layer 423 and theinterlayer insulating film 111. The wiring layer 424 is, for example, acopper (Cu) layer or an aluminum (Al) layer. The wiring layer 424 iscovered with the interlayer insulating film 112.

As described above, the via-plug 400 a of FIG. 8 has the same structureas that of the contact plug 100 of FIG. 1. Thus, according to theembodiment, similarly to the first embodiment, it is possible to realizea contact plug with low resistance and low cost. The semiconductordevice of the embodiment can be manufactured by the same manufacturingmethod as that of the semiconductor device of the first embodiment.

The via-plug 400 a of the embodiment may have the same structure as thatof the contact plug of FIG. 2.

The gate electrode 402 of the embodiment may be a semiconductor layerother than a silicon layer, similarly to the case of the substrate 101of the first embodiment. The gate electrode 402 of the embodiment may bea laminated film including a metal layer and a semiconductor layerformed on the metal layer.

FIG. 9 illustrates a structure of a semiconductor device of a fourthembodiment, which focuses a via-plug constituting the semiconductordevice.

A wiring layer 124 a of FIG. 9 is different from the wiring layer 124 ofFIG. 7, and is not a polysilicon layer but a metal layer. Accordingly,when the semiconductor device of FIG. 9 is manufactured, diffusion ofsilicon (Si) atoms from the wiring layer 124 a to a MoON film 312 doesnot occur. As a result, the semiconductor device of FIG. 9 does not havea layer and a film corresponding to the molybdenum (Mo) containing layer301 and the MoSiON film 311 shown in FIG. 7. According to theembodiment, it is possible to cover a bottom portion and a side surfaceof a contact hole H₂ with a barrier metal layer of the MoON film 312.

Various materials may be used as a metal material forming the wiringlayer 124 a. A molybdenum containing layer may be formed in the surfaceportion of the wiring layer 124 at the bottom portion of the contacthole H₂, depending on the kinds of the metal materials.

The wiring layer 124 a may be, for example, a laminated film including asemiconductor layer and a metal layer formed on the semiconductor layer.

FIG. 10 illustrates a structure of a semiconductor device of a fifthembodiment, which focuses a MOSFET constituting the semiconductordevice.

The semiconductor device of FIG. 10 has a substrate 101 and aninterlayer insulating film 111, and a gate insulating film 401, a gateelectrode 402, a side wall insulating film 403, and a source/draindiffusion layer 404 constituting the MOSFET.

As illustrated in FIG. 10, the gate electrode 402 includes asemiconductor layer 501 formed as a first electrode material, a MoSi_(X)layer 502, a MoSiON film 511, a MoON film 512, and a metal layer 513formed as a second electrode material. The gate electrode 402 is alaminated body serving as an electrode.

The semiconductor layer 501 is formed on the substrate 101 via the gateinsulating film 401. The semiconductor layer 501 is, for example, apolysilicon layer. The gate electrode 402 of the embodiment is apoly-metal gate including a polysilicon layer 501 and a metal layer 513as first and second electrode materials.

The MoSi_(X) layer 502 is formed on a surface of the semiconductor layer501. The MoSi_(X) layer 502 is a molybdenum containing layer. The MoSiONfilm 511, the MoON film 512, and the metal layer 513 are formed in thisorder on the MoSi_(X) layer 502. The MoSiON film 511 and the MoON film512 are a barrier metal layer containing molybdenum. The metal layer 513is, for example, a molybdenum (Mo) layer. As another example of themetal layer 513, a layer containing at least any one of Mo, Cu, Al, W,Ru, and Ta may be used.

As described above, in the embodiment, the barrier metal layer iscomposed of the MoSiON film 511 and the MoON film 512, and the metallayer 513 is a molybdenum layer. Any of the MoSiON film, the MoON film,and the metal layer 513 has low resistance. Thus, according to theembodiment, it is possible to realize a gate electrode with lowresistance. Molybdenum is available at a relatively low cost. Thus,according to the embodiment, it is possible to realize a gate electrodeat a low cost. Any of the MoSiON film 511 and the MoON film 512 asbarrier metal layers and the metal layer 513 are mainly based onmolybdenum. According to the embodiment, it is possible to furtherreduce the cost of manufacturing a gate electrode.

The structure of the gate electrode 402 of the embodiment as a laminatedbody may be also applied to a floating gate of a NAND-type memory, acontrol gate, or an interconnection of a ReRAM or a PCRAM with across-point structure.

A method of manufacturing method of the semiconductor device of thefifth embodiment will be described with reference to FIG. 11A to FIG.11F.

FIGS. 11A to 11F are cross-sectional views illustrating the method ofmanufacturing the semiconductor device of the fifth embodiment.

As illustrated in FIG. 11A, a gate insulating film 401 is formed on asubstrate 101 by thermal oxidation or CVD. The gate insulating film 401is, for example, a silicon dioxide film. In addition, a semiconductorlayer 501 is formed on the gate insulating film 401 by CVD. Thesemiconductor layer 501 is, for example, a polysilicon layer into whichP-type impurities or N-type impurities are doped.

Then, a MoN film 601 is laminated on the semiconductor layer 501 by PVD,CVD or ALD. The surface of the MoN film 601 is oxidized to form aMoO_(X) film 602 on a surface of the MoN film 601. The laminated filmincluding the MoN film 601 and the MoO_(X) film 602 is a barrier metallayer containing molybdenum.

The oxidation process for the surface of the MoN film 601 is performedat the same temperature as that of the lamination process of the MoNfilm 601, for example, at a temperature equal to or higher than 400° C.Hereinafter, a heat treatment at the oxidation process is referred to asa first heat treatment, similarly to the first embodiment.

Then, as illustrated in FIG. 11B, a heat treatment for a substrate 101is performed at a temperature higher than that of the first heattreatment, for example, at a temperature equal to or high than 500° C.As a result, a MoSi_(X) layer 502 is formed between the semiconductorlayer 501 and the barrier metal layer. The MoN film 601 and the MoO_(X)film 602 are changed into the MoON film 512 by the heat treatment, andsilicon contained in the semiconductor layer 501 is diffused into theMoON film 512. Consequently, a MoSiON film 511 is formed between theMoSi_(X) layer 502 and the MoON film 512. Hereinafter, the treatment isreferred to as a second heat treatment similarly to the firstembodiment.

The first heat treatment and the second heat treatment may be integratedinto one heat treatment similarly to the first embodiment.

Then, as illustrated in FIG. 11C, a metal layer 513 is laminated on theMoON film 512 by CVD. In addition, a mask layer 611 is formed on themetal layer 513 by CVD. The mask layer 611 is, for example, a siliconnitride film.

As illustrated in FIG. 11D, patterning of the mask layer 611 isperformed by lithography and etching.

Then, as illustrated in FIG. 11E, the metal layer 513, the MoON film512, the MoSiON film 511, the MoSi_(X) layer 502, and the semiconductorlayer 501, which are conductive layers, are etched using the mask layer611. As a result, a gate electrode 402 which is composed of thelaminated conductive layers is formed on the substrate 101 via the gateinsulating film 401.

As illustrated in FIG. 11F, a side wall insulating film 403 is formed ona side surface of the gate electrode 402. Then, in addition,source/drain diffusion layers 404 are formed in a surface region of thesubstrate 101 so as to interpose the gate electrode 402.

Then, various contact plugs, via-plugs, wiring layers, and interlayerinsulating films are formed. In such a manner, the semiconductor deviceof FIG. 10 is manufactured.

As described above, in the embodiment, the MoN film 601 and the MoO_(X)film 602 are formed in this order on the semiconductor layer 501, andthe barrier metal layer is formed by the MoN film 601 and the MoO_(X)film 602. Thus, according to the embodiment, it is possible to suppressforming a SiN film between the semiconductor layer 501 and the metallayer 513.

A semiconductor other than silicon may be used as the semiconductorlayer 501. A silicon germanium layer may be used as the semiconductorlayer.

Modifications of a semiconductor device of the fifth embodiment will bedescribed with reference to FIGS. 12A to 12C.

FIGS. 12A to 12C are cross-sectional views illustrating structures ofthe modifications of the fifth embodiment.

In FIG. 12A, a gate electrode 402 has a MoSiN film (a molybdenum siliconnitride film) 621, a MoN film 601 and a MoO_(X) film 602 as conducivefilms between a MoSi_(X) layer 502 and a metal layer 513. For example,the gate electrode 402 having the conductive films may be formed byperforming the second heat treatment of FIG. 11B, under a condition inwhich change from the MoN film 601 and the MoO_(X) film 602 into theMoON film 512 is suppressed. For example, in the step of FIG. 11B, thesecond heat treatment may be performed at 400 to 500° C. to form suchthe gate electrode 402. The MoSiN film 621 is formed by diffusion ofsilicon contained in the semiconductor layer 501 into the MoN film 601.The MoSiN film 621 is a barrier metal layer containing molybdenum.

In FIG. 12B, a gate electrode 402 has a MoSiN film 621 but does notinclude a MoN film 601 and a MoO_(X) film 602, between the MoSi_(X)layer 502 and the metal layer 513. The gate electrode 402 can be formedby performing the second heat treatment under the same condition as thatof a method of manufacturing the semiconductor device of FIG. 12A, andthen by performing a reduction treatment of the MoO_(X) film 602 and adesorption treatment of molybdenum and nitrogen contained in the MoNfilm 601. Resistance of the gate electrode 402 of FIG. 12B may be lowerthan that of the gate electrode 402 of FIG. 12A.

In FIG. 12C, a gate electrode 402 has a MoSiN film 621 and a MoN film601 but does not include a MoO_(X) film 602, between a MoSi_(X) layer502 and a metal layer 513. The gate electrode 402 may be formed byperforming the second heat treatment under the same condition as that ofthe method of manufacturing the semiconductor device of FIG. 12A andthen by performing a reduction treatment of the MoO_(X) film 602.Alternatively, the gate electrode 402 may be formed by performing thesecond heat treatment after forming the metal layer 513 without formingthe MoO_(X) film 602 in the step of FIG. 11B. Resistance of the gateelectrode 402 of FIG. 12C can be lower than resistance of the gateelectrode 402 of FIG. 12A.

FIG. 13 illustrates an example in which the fifth embodiment is appliedto a NAND-type memory. A semiconductor device of FIG. 13 has a substrate101, an interlayer insulating film 111, a cell transistor 701, and adiffusion layer 702.

The cell transistor 701 includes a gate insulating film 711, a floatinggate 712, an inter-gate insulating film 713 and a control gate 714 whichare formed on the substrate 101 in this order. The control gate 714includes a semiconductor layer 714 a, a MoSi_(X) layer 714 b, a MoSiONfilm 714 c, a MoON film 714 d, and a metal layer 714 e which are formedon the floating gate 712 via the inter-gate insulating film 713 in thisorder.

The control gate 714 is a laminated body serving as an electrode. Asdescribed above, the semiconductor device of the fifth embodiment may bealso applied to the NAND-type memory.

In the fifth embodiment, the barrier metal layer containing molybdenumis formed between the semiconductor layer 501 and the metal layer 513constituting an electrode or an interconnection. Thus, according to theembodiment, it is possible to provide an electrode or aninterconnections with low resistance and low cost, similarly to thefirst to fourth embodiments.

The metal layer 513 may be the molybdenum (Mo) layer or any other thanthe molybdenum layer. However, when the metal layer 513 is themolybdenum layer, the molybdenum layer shows an advantage that a meltingpoint is high. A melting point of the molybdenum layer is equal to orhigher than 1000° C. Generally, as to a gate electrode of a DRAM or aNAND-type memory and a cross-point interconnection of a ReRAM or aPCRAM, it is required that the melting point is high, and thus it isappropriate to use the molybdenum layer as the metal layer 513.

When the metal layer 513 is formed, it is preferable to adjust anannealing condition of the metal layer 513 so as to increase diametersof crystal grains of the metal layer 513. By the adjustment of theannealing condition, it is possible to lower the resistance of the metallayer 513 further. Such adjustment may be also applied to the plugmaterial layers 123, 313, 423 of the first to fourth embodiments.

The semiconductor devices according to the first to fourth embodimentsand the modifications of the embodiments described above may bemanufactured by forming an interlayer insulating film on a substratecontaining silicon or on a conductive layer containing silicon formed ona substrate, forming a hole reaching the substrate or the conductivelayer in the interlayer insulating film, forming a barrier metal layercontaining molybdenum on a bottom surface and a side surface of thehole, forming a molybdenum containing layer in the substrate or theconductive layer at a bottom portion of the hole by a heat treatment ofthe substrate, diffusing silicon contained in the substrate or theconductive layer into the barrier metal layer at the bottom surface ofthe hole, and forming a plug material layer in the hole via the barriermetal layer.

The barrier metal layer formed on the bottom surface and the sidesurface of the hole is a laminated film including the molybdenum nitridefilm and the molybdenum oxide film. The molybdenum oxide film is formedby oxidizing a surface of the molybdenum nitride film at a temperatureequal to or higher than 400° C. In this case, in the heat treatment forforming the molybdenum containing layer, the substrate may be heated at500° C. or higher. The molybdenum oxide film can be formed by the heattreatment for forming the molybdenum containing layer.

For example, the semiconductor devices according to the fifth embodimentand the modifications of the fifth embodiment are manufactured byforming a semiconductor layer containing silicon as a first wiringmaterial or as an electrode material on a substrate, forming a barriermetal layer containing molybdenum on the semiconductor layer, forming amolybdenum containing layer between the semiconductor layer and thebarrier metal layer by a heat treatment of the substrate, diffusingsilicon contained in the semiconductor layer into the barrier metallayer, forming a metal layer as a second wiring material or as anelectrode material on the barrier metal layer, and processing thesemiconductor layer, the molybdenum containing layer, the barrier metallayer and the metal layer so as to form a laminated body serving as aninterconnection or an electrode.

While certain embodiments have been described, these embodiments havebeen presented by way of example only, and are not intended to limit thescope of the inventions. Indeed, the novel embodiments described hereinmay be embodied in a variety of other forms. Furthermore, variousomissions, substitutions and changes in the form of the embodimentsdescribed herein may be made without departing from the spirit of theinventions. The accompanying claims and their equivalents are intendedto cover such forms or modifications as would fall within the scope andspirit of the inventions.

What is claimed is:
 1. A semiconductor device comprising: an interlayer insulating film which is formed on a substrate or on a conductive layer containing silicon formed on a substrate, the interlayer insulating film having a hole reaching the substrate or the conductive layer; a molybdenum containing layer formed on the substrate or in the conductive layer at a bottom portion of the hole; a barrier metal layer formed on the molybdenum containing layer and on a side surface of the hole, a portion of the barrier metal layer formed on the side surface containing at least molybdenum, a portion of the barrier metal layer formed on the molybdenum containing layer including at least a molybdenum silicate nitride film; and a plug material layer formed in the hole through the barrier metal layer.
 2. A semiconductor device comprising: an interlayer insulating film which is formed on a substrate containing silicon or on a conductive layer containing silicon formed on a substrate and, the interlayer insulating film having a hole reaching the substrate or the conductive layer; a barrier metal layer formed on a bottom portion and a side surface of the hole, a first portion of the barrier metal layer formed on the side surface containing at least molybdenum, a second portion of the barrier metal layer formed on the bottom portion containing at least molybdenum and silicon; and a plug material layer formed in the hole through the barrier metal layer.
 3. The semiconductor device according to claim 2, further comprising a molybdenum containing layer which is formed on the substrate or in the conductive layer at a bottom portion of the hole so as to be in contact with the second portion of the barrier metal layer.
 4. The semiconductor device according to claim 2, wherein the second portion of the barrier metal layer includes a molybdenum silicate nitride film.
 5. The semiconductor device according to claim, 4, wherein the molybdenum silicate nitride film is formed on the bottom portion and on a portion of the side surface of the hole.
 6. The semiconductor device according to claim 2, wherein the plug material layer contains at least any one of molybdenum, copper, aluminum, tungsten, ruthenium, or tantalum.
 7. The semiconductor device according to claim 2, further comprising a wiring layer which is formed on the plug material layer and the interlayer insulating film, and is formed of the same material as that of the plug material layer is further included.
 8. The semiconductor device according to claim 3, wherein the second portion of the barrier metal layer includes a molybdenum silicate nitride film.
 9. The semiconductor device according to claim 4, wherein the first portion of the barrier metal layer includes a molybdenum oxynitride film.
 10. The semiconductor device according to claim 8, wherein the first portion of the barrier metal layer includes a molybdenum oxynitride film.
 11. The semiconductor device according to claim 4, wherein the molybdenum containing layer is a molybdenum silicide layer.
 12. The semiconductor device according to claim 9, wherein the first portion of the barrier metal layer includes a molybdenum oxynitride film and molybdenum oxide film.
 13. A semiconductor device comprising: a substrate; and a laminated body formed on the substrate and serves as an interconnection or an electrode, wherein the laminated body includes a semiconductor layer containing silicon which is formed as a first wiring material or an electrode material above the substrate, a barrier metal layer which is formed on the semiconductor layer and contains molybdenum, and a metal layer which is formed on the barrier metal layer as a second wiring material or an electrode material.
 14. The semiconductor device according to claim 13, wherein the laminated body further includes a molybdenum containing layer between the semiconductor layer and the barrier metal layer.
 15. The semiconductor device according to claim 14, wherein the molybdenum containing layer is a molybdenum silicide layer.
 16. The semiconductor device according to claim 13, wherein the barrier metal layer includes a molybdenum silicate nitride film.
 17. The semiconductor device according to claim 15, wherein the barrier metal layer includes a molybdenum silicate nitride film. 